Novel antifoggant for silver halide emulsion on a polyester film support

ABSTRACT

A LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL WHICH COMPRISES A POLYESTER FILM SUPPORT AND, COATED THEREON, A LIGHT-SENSITIVE SILVER HALIDE EMULSION, AT LEAST ONE LAYER OF SAID PHOTOGRAPHIC MATERIAL CONTAINING A NEW ANTIFOGGANT SPECIFIED LATER. THE SAID ANTIFOGGANT PREVENTS THE IMPURITIES IN THE POLYESTER FILM SUPPORT FROM FOGGING THE SILVER HALIDE EMULSION DURING ITS STORAGE OR INCUBATION.

United States Patent Int. (:1. aim 1/34 US. Cl. 96-109 3 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide photographic material which comprises a polyester film support and, coated thereon, a light-sensitive silver halide emulsion, at least one layer of said photographic material containing a new antifoggant specified later. The said antifoggant prevents the impurities in the polyester film support from fogging the silver halide emulsion during its storage or incubation.

This invention relates to a light-sensitive silver halide photographic material which comprises a polyester film support and, coated thereon, a light-sensitive silver halide photographic emulsion, at least one layer of said photographic material containing a new antifoggant specified later.

Recently, polyester film has been brought into wide use as a support for a photographic element instead of cellulose triacetate film, because of excellent physical properties of the former. However, the polyester film disadvantageously contains a variety of byproducts, catalyst residues and other impurities, among which certain compounds usually cause very severe fogging on a light-sensitive silver halide photographic emulsion during its storage or incubation. Even if these byproducts, catalyst residues, etc. can be removed through an improved process for the production of polyester film, it is still unavoidable to prevent the self-decomposition of polyester with the result that the resulting decomposition products possibly cause increased fog on the emulsion. Thus, it is very difficult to remove any fogging factors from a polyester film support at the stage of its preparation. As the consequence, it becomes necessary for the preparation of a light-sensitive silver halide photographic material using a polyester support to incorporate a suitable antifoggant into various layers coated on the support, e.g. sub layer, inter layer, emulsion layer, protective layer, etc. Unfortunately, however, any antifoggant suited for this purpose has not yet been known.

It is accordingly one object of this invention to provide a light-sensitive silver halide photographic material with a polyester film support, said material being freed from fogging due to the action of the polyester film support. In order to accomplish this object, we have now found a new antifoggant which when incorporated into the sub layer, inter layer, emulsion layer and/or protective layer of a light-sensitive silver halide photographic material is highly effective to prevent fogging due to the action of a polyester film support of saidmaterial. 'Iheantifoggants used in the present invention can be represented by the antifoggants include the following compounds which are listed below only for illustration.

( HOCH SO NS.

( HO ousoma (3) HOC|]H-SO3K HO OHSOgNS.

(5) HO CHSOsNa Cn as HO (IJHSO Na OH- (7) HO (CH2)2SO3K (8) HO (CHzhSO Na HO CHSOQNZI (10) HO (llHsOaNa.

l C O OH (11) HO (|JHSO3Na,

| SOsNfi.

( HO (CH2)4SO NH4 (13) HO(CH2)B O3K SYNTHESIS OF THE COMPOUND 2 11.4 g. of n-hexyl aldehyde dissolved in 60 m1. of ethanol is added to 10.4 g. of sodium bisulfite dissolved in ml. of water. The resulting mixture is allowed to stand overnight at room temperature and then heated under reflux on a water bath for 4 hours. The reaction mixture which is pale yellow and clear is distilled under reduced pressure. The white crystalline residue obtained is dissolved in a water-methanol mixture and then the solution is added with ether. The precipitate formed is collected by filtration and dried under reduced pressure. The white crystalline product is the Compound 2. Yield 9.5 g. M.P. 300 "C.

SYNTHESIS OF THE COMPOUND 4 To 11 g. of sodium bisulfite dissolved in ml. of water, 13.8 g. of 3,4-dihydroxybenzaldehyde is added, with stirring. The resulting solution is allowed to stand overnight and then heated under reflux on a water bath for hours. The reaction mixture is concentrated and the brown crystalline mass separated is taken up into 400 ml. of methanol. The resulting solution is heated under reflux 4 polyester film support. In contrast to this, use of the Compound 2 can minimize the fog during high temperature incubation as little as that which is observed in the con- 'ventional photographic film using cellulose triacetate and then filtered while it is hot. The filtrate is concentrated 5 support. Further, photographic properties of film samples once again. The crystalline residue is washed with an just after their preparation indicate that the Compound 2 ethanol-ether mixture and then dried in vacuo. The brown has no adverse influence on the properties. It is clear that crystalline product is the Compound 4. Yield 9.9 g. M.P. the Compound 2 is effective against fogging due to the 300 C. use of polyester film support.

Any one of the above-indicated compounds is added to EXAMPLE 2 a light-sensitive silver halide photographlc emulsion at the proportion f 5 1() t 5 1O l per l of A light-senslti-ve gelatinous S11Vel' halide photographic silver halide in the emulsion. Alternatively, the selected emulsion, which contains 100 of Silver iodobromide compound may be incorporated into an inter layer, sub with the content of 11101 P is Subjected to layer and/ or protective layer at the amount of 10- to 10- 15 second ripening with gold sensitization. After completion l per square f h s f ce f h finished li htof said second ripening, the emulsion subjected to optical sensitive photographic material. Use of the compounds in sensitization. This emulsion is then added with 1,2-benz-5- the excess amount should be avoided, as this causes extray Y Y- and then W h formaordinary fogging during storage or heat treatment of th lin and saponin. The resulted emulsion is divided into emulsion. Light-sensitive silver halide photographic emulfour Portions, two of Which re load d with the Comsions which may be employed in the present invention in- Pound 9 and Other t a not 0. One of the unloaded clude any conventionally known ones, e.g. silver bromide, emulsions is coated on cellulose triacetate film support. silver iodobromide, silver chloride, silver chlorobromide The r maining three portions are individually coated on or the like emulsions. It should be noted that compounds p yester film support. .After drying of the coated u of the above general formula where n is taken for more ports, there are obtained four light-sensitive photographic than 8 are substantially ineffective for the intended fi s Which e then subjected to sensitometry according purpose to the HS method K4604. The results of sensitometric New antifoggants disclosed in this application are entests are et for h i Table 2. tirely different in their chemical structure and fguliction TABLE 2 from any conventionally known inhibitors and sta i izers. The antifoggants can be used singly or in combination with gi gj g ?fg the known inhibitors and stabilizers. Further, coloring preparation RH i'orfidays materials, color formers, sensitizers, hardnlelrs or ether cgmp fi nd Rep? a; known agents for a silver halide photograp ic emu sion P five ve also can be used together with the antifoggants disclosed Support AEX Speed Tog sp ed 1min- 8-93 22 8t? Now the present invention will be explained in detail 95 with reference to the following examples. (109 95 12 130 EXAMPLE 1 40 As apparent from the above, the film sample prepared A light-sensitive gelatinous silver halide photographic by coating the loaded emulsion on polyester film support emulsion, which contains 100 g. of silver iodobromide with is entirely free from fogging during incubation t the AgI content of 1.5 mil percent, is subjected to second 55 C. ripening with gold sensitization. Immediately after corn- EXAMPLE 3 pletion of said second ripening, the emulsion is added with A light senshive gelatinous silver halide photographic an aqueous Solutloh 0f P emulsion, which contains 100 g. of silver iodobromide 3,4,7a-trlalalndene and an alcohfllc of y with the AgI content of 5.3 mol percent, is subjected to 5me1'capt0- l h e W1 th formahn P saPomn' second ripening with gold sensitization. Immediately after The resulted emulsion is divided into four portions, two of completion of Said second ripening the emulsion is added which are loaded with the Compound 2 and other two are with 1g2 benz 5 methyl 7 hydroxy 3,4,7a triazaihdehe not so. One Of th unloaded emulslon? coated on formalin and saponin. The resulted emulsion is divided lose triacetate film support. The remaining three portions into four portions, two of which are loaded with the are 1nd1v1dually coated in polyester film support. After Compound 6 and other two are not one of the drying Of t e Coated supports, there obtalned loaded emulsions is coated on cellulose triacetate film hght'sehsltlve Photographlc P Whlch are then support. The remaining three portions are individually ected to eehsltometfy acQordmg. to the HS mCthQd coated on polyester film support. After drying of the coated K-7604. The results of sensitometric tests are set forth 111 supports there are Obtained f fighhsensitive photm Table 1. TABLE I graphic films which are then subjected to sensitometry according to the JIS method K-7604. The results of sensilmm diat y Incubated tometric tests are set forth in Table 3.

after 55 C. under 5% preparation RH for 5 days TABLE 3 3%; etr seepa e Support .AgX (g.) Fog speed Fog speed preparation RH for 5 days Cellulosetriacetate- 0. 07 100 0.11 120 Compound 0 2a .22 39% "11-. S 60 D3111: 210 0107 0112 AEX g speed Fog peed Cellulose triacetate 0. 08 100 0. 12 Polyester 0. 09 95 0. 40 As apparent from the above, the film sample prepared 70 D 91% 8 35 8: by coating the unloaded emulsion on polyester film sup- 7 port suffers from very serious fogging during the incuba- As apparent from the above, the film sample prepared fiOh at ThiS means that 1, Yl-7-hyby coating the loaded emulsion on polyester film support droxy-3,4,7a-triazaindene and 1-phenyl-5-mercapto-tetrais entirely free from fogging during the incubation at zole are not efiective against fogging resulting from 75 55 C.

EXAMPLE 4 To an aqueous gelatine solution, formalin and saponine are added. Then this solution is divided into two portions, one of which is added with the Compound 8 and As apparent from the above, addition of the Compound 1 into the photographic emulsions is entirely satisfactory to prevent fogging due to polyester film support during high temperature incubation and normal storage.

then coated on polyester film support, while the other is 5 EXAMPLE 6 ggfi i f ggggg if of the Compound on poly This eirample shows application of the invention to a Separately, a light-sensitive gelatino silver halide photohggt'sensmve (iolor'photogi'aphlc material graphic emulsion containing 100 g. of silver iodobromide compoun 0 t 6 0mm a with the AgI content of 1.5 mol percent is subjected to 10 second ripening with gold sensitization and then added with an aqueous solution of l,2-benz-5-methyl-7-hydroxy- 3): 3,4,7a-triazaindene and an alcoholic solution of l-phenyl- N NHC0C15H.-.1C1O4 .S-mercaptotetrazole and then with formalin and saponin. g This emulsion is coated on the polyester film supports as 2 prepared aobve. For comparison, the same emulsion is coated directly on cellulose triacetate film support to give a control Sample is formed into a 3% methanol solution To a greenl photographlc.films ai prepares are Subjected to sensitive high sensitivity color photographic silver brosensltometry accordmg.to e Hs'met 0d K4604 The mide emulsion, the above-mentioned solution is added test results are Set forthm Table in an amount of 30 cc. per liter of said emulsion. This TABLE 4 emulsion is then incorporated with a solution prepared lmmefgiately lnccubatgd 7 by dissolving1 in ahl N carilstic soda solutlion, 15 of Elle 8 er erfi o inner-type co or p otograp ic magenta co or coup er w M carboxyphenyl) 3 (4-palmitoylamino-benzoylamino)- zlf il i 5-pyrazolone, and the pH of this emulsion is adjusted to Support lmerlayer Fog Speed Fog Speed 6.8 e(rineantsl oil; cigic acid. CThe thus lprepared emulsion is a wit t e ompoun 8 and t en coated onto a filtttliiffttiiitlfi: 833315 543511 31%; 133 31%;? .1??? p s/ r fi m pr and r e g l g fi m is a M- su jecte to entire y t e same test as in Xam e to- Do tiijfigfi 105 120 gether with a sample film to which the Compofnd 8 has been added. Provided that, in this case, the treatments are carried out according such ordinary procedures that As apparent from the above, the simple interlayer is the films are developed by use of a color developer connot elfective to prevent unusual fogging due to the polytaining diethyl-p-phenylenecliamine and are then subjected ester film support, whereas incorporation of the Comto water-washing, bleaching, water-washing, fixing, waterpound 8 into the inter layer is satisfactory for the intended washing and drying. As the result, it was found and folpurpose. lows from the aforesaid that the light-sensitive silver ha- EXAMPLE 5 40 lide color photographic material containing Compound 8 according to the present invention was completely free A light-Sensitive gelatinous Silver halide Photographic from undesired fogging due to the polyester film support emulsion, Which Contains 100 of Silver iOdObIOmide whereas the film without Compound 8 exhibited serious with the AgI content of 1.5 mol percent, is subjected to f i second ripening with gold sensitization. Immediately after Wh t we l i i Completion of Said Second ripening, the emulsion is added 1. A light-sensitive silver halide photographic material with an aqueous Solution of Y Y comprising an emulsion layer and a polyester film support 3,4,7a-triazaindene and an alcoholic solution of l-phenylcontaining a compound of the general formula S-mercapto-tetrazole and then with polyethylene glycol (average molcular weight 2000), formalin and saponin. The resultant emulsion is divided into four portions, tWo of which are loaded with the Compound 1 and other two HO(CHZ)$H'SOQM are not so. One of the unloaded emulsions is coated on R cellulose triacetate film support. The remaining three portions are individually coated on polyester film support. After drying of the coated supports, there are obtained where n is an integer of 0 to 7, R is a hydrogen atom or four light-sensitive photographic films which are then suban alkyl group of not more than 17 carbon atoms, a jected to sensitometry according to the JIS method phenyl group or a naphthyl group which may be sub- K-7604. The results of sensitometric tests are not forth stituted with hydroxyl, carboxyl or sulfo groups, and M in Table 5. is an alkali metal or ammonium cation, the compound TABLE 5 Immediately Incubated at 55 after prepara- C. under 5% After storage tion for 5 days over 3 months Compound Rela- Rela- Rela- 1 per g. tive tive tive upport AgX (g.) Fog speed Fog speed Fog speed Cellulose triacetate 0. 10 0. 15 130 0.12 Polyester 0. 12 90 0.80 1. 13 D 0. 09 100 0.14 0.12 100 0. 09 100 0.13 0.11 105 being added in the proportion of 5 X 10-" to 5 1O mole as claimed in claim 1, wherein it is a light-sensitive silver per mole of silver halide or in an amount of 10* to halide color-photographic material. 10- mole per square meter of surface of the light-sensitive photographic material which compound prevents fog- References Cited ging of the layer containing silver halide. 5 FOREIGN PATENTS 2. A light-sensitive s11ver halide photographic materlal as claimed in claim 1, wherein the incorporation of said 1,341,010 9/1963 France 96109 cm d lid'th b1 ,'t1 /0 g flig f 5;? R m e ayer er ayer and r NORMAN G. TORCHIN, Primary Examiner 3. A light-sensitive silver halide photographic material 10 W. H. LOUIE, Ira, Assistant Examiner 

